中文摘要
高效液相層析（HPLC）及毛細管電泳（CE）同屬液相層析技術，分別遵循不同的分離機制，各有優缺點，為目前最常用來定量中藥成分的方法。本研究的目的在於開發HPLC與CE方法，尋找最適化條件，以分析川芎與當歸之有機酸含量，並比較該兩種方法的優劣。同時，利用分析的結果，進行川芎與當歸之基原化學辨識。
川芎與當歸均為常用中藥材，前者具有鎮靜、活血袪瘀、袪風止痛的功能，後者具鎮靜、活血、補血、調經等功能，都含有精油、胺基酸、脂肪酸、有機酸、糖類等成分；其中，有機酸以nicotinic acid(NA)、phthalic acid(PH)、protocatchuic acid(PR)、folic acid(FL)、folinic acid(FN)、p-hydroxybenzoic acid(HB)、vanillic acid(VA)、caffeic acid(CA)、ferulic acid(FA)為主要組成。本文用逆向毛細管區帶電泳層析(reversed EOF CZE)分析技術，以9 mM Na2B4O7，2 mM NaH2PO4，10 mM LTAC(pH=9.56)及CH3CN（7:3,v/v）為緩衝溶液，在25℃， -25kV及210 nm下，於25分鐘之內成功分析這九個有機酸成分；在HPLC部分，使用30mM KH2PO4與CH3CN（8:2,v/v）為沖提液，以10％H3PO4調整pH=3.50，可於60分鐘之內成功分析這九個有機酸成分。比較兩者分析結果發現，在分析時間、偵測極限及樣品注射量上，以CE為優，但在再現性及理論板數方面，則以HPLC較好。
我們從台灣、日本及大陸共收集28件川芎樣品與32件當歸樣品，經顯微鏡檢確認其中計有川芎（Ligusticum chuanxiong Hort）21件、日芎（Cnidium officinale Makino）7件；川當歸(Angelica sinensis Diels.)10件、北海道日本當歸（A. acutiloba Kitagawa var. sugiyamae Hikino）6件、韓國土當歸（A. gigas Nalai）6件、大深當歸（A.acutiloba Kitagawa）10件，進行川芎與當歸之基原化學辨識研究。結果發現，川芎與日芎可用化合物1、5、6、7等波峰辨別：L. chuanxiong無化合物5（p-hydroxybenzoic acid）；7/6比值：L. chuanxiong＜2.5，C. officinale＞2.9；1/6比值：L. chuanxiong＜1.5，C. officinale＞2.1。不同品種當歸可用化合物2、3、4、5 6、8、9等波峰分辨：A.sinensis無5及6；3/2比值＞3.5為A. acutiloba var. sugiyamae；4/5比值＞20為A.acutiloba；9/8比值＞18為A. gigas。川芎為活血去瘀藥，當歸為補血藥，是重要的藥對，常合併使用。本文綜合川芎與當歸的分析數據，可明確分辨兩藥材共計六種植物的基原。

Abstract
Both high-performance liquid chromatography (HPLC) and capillary electrophoresis (CE) belong to chromatographic technique, each following a different separation mechanism with superiorities and inferiorities of their own, and are the most commonly used methods for analyzing Chinese herb drug components. This study is aimed to develop HPLC and CE methods with the most-optimized conditions for analyzing the contents of organic acids in Cnidii Rhizoma and Angelicae Radix and to compare the advantage as well as the drawback of both methods. Meantime, the analytical results are used for chemotaxonomic identification of both herb drugs.
Cnidii Rhizoma and Angelicae Radix are commonly used Chinese herb drugs. The former possesses tranquilizing, blood enlivening, hemostasis-resolving, anemofugic and analgesic effects; and the latter possesses tranquilizing, blood enlivening, hemopoietic and menstrual regulating effects. Both drugs contain essential oils, amino acids, fatty acids, organic acids and sugars. The organic acids comprose chiefly of nicotinic acid (NA), phthalic acid (PH), protocatchuic acid (PR), folic acid (FL), folinic acid (FN), β-hydroxybenzoic acid (HB), vanilic acid (VA), caffeic acid (CA) and ferulic acid (FA). In this study, we used the reversed EOF CE technique with 9 mM Na2B4O7, 2 mM NaH2PO4, 10 mM LTAC (pH=9.5) and CH3CN (7:3, v/v) as the buffer solution, at 25℃, -25 kV and 210 nm, to have successfully separated the nine acid compounds. In the part of HPLC, 30 mM KH2PO4 and CH3CN (8:2, v/v) served as the eluent, adjusted to pH3.5 with 10% H3PO4, which enabled us to successfully analyze nine organic acids within 60 min. Comparing the analysis results of both methods, we found that CE was superior in terms of analysis time, detection limit and quantity of sample injected；but in reproducibility and theoretical plate number, HPLC was better.
From Taiwan, Japan and mainland China, we collected 28 samples of Cnidii Rhizoma and 32 samples of Angelicae Radix. Preliminary microscopic identification found 21 samples belonging to Szechuanese cnidium of China (Ligusticum chuanxiong Hort); 7 samples, Japanese cnidium (Cnidium officinale Makino); 10 samples, Szechuanese angelica (Angelica sinensis Diels); 6 samples, Hokkaido angelica of Japan (A. acutiloba Kitagawa var. Sugiyamae Hikino); 6 samples, indigenous angelica of Korea (A. gigas Nalai); and 10 samples, Oshin angelica of Japan (A. autiloba Kitagawa). As a result of Chemotaxonomic identification, it was found that the Szechuanese cnidium and Japanese cnidium could be identified by the absorption peaks of compounds 1, 5, 6 and 7 in that the Szechuanese cnidium (L. chuanxiong) did not have compound 5 (p-hydroxybenzoic acid); the 7/6 ratio was < 1.5 for L. chuanxiong and >2.9 for C. officinale; the 1/6 ratio was <1.5 for L. chuanxiong, and >2.1 for C. officinale. Different species of Angelica can be distinguished by means of the peaks ratio of compounds 2, 3, 4, 5, 6, 8 and 9, whereby A. sinensis did not have 5 and 6; 3/2 ratio was >3.5 for A. acutiloba var. sugiyamae; 4/5 >20 for A. acutiloba; and 9/8 >18 for A. gigas. Cnidii Rhizoma is a blood enlivening and hemostasis-eliminating drug and Angelicae Radix, a hemopoietic drug; both herbs are often combined as an herb couple important in a variety of indications in traditional Chinese medicine. In this study, we combined the analysis data of Cnidii Rhizoma and Angelicae Radix for identifying the two herbs from six different botanical sources.

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